Chiral Phosphite-Thioether Complexes of Palladium(0). Comments on the Pd, Rh, and Ir Regio-and-Enantioselective Allylic Alkylations of PhCH=CHCH(OAc)R, R = H, Me, Et

Kumaravel Selvakumar, Massimiliano Valentini, Paul S. Pregosin, Alberto Albinati

Research output: Contribution to journalArticle

88 Citations (Scopus)

Abstract

The new chiral auxiliary (R)-2-ethylthio-1-(phenylethyl)-(R)-binaphthyl phosphite, 1, and three stable Pd(0) olefin complexes containing this chelate, 2-4, have been synthesized. The structure of the maleic anhydride complex 3 has been determined by X-ray diffraction methods. Solution details for 2-4 and aspects of their dynamics have been elucidated via 2-D NMR spectroscopy. The fumaronitrile complex 2 exchanges intramolecularly, whereas the maleic anhydride and pentenedione derivatives, 3 and 4, respectively, exchange intermolecularly. Ligand 1 has been used as auxiliary in the Pd, Rh, and Ir regio- and enantioselective allylic alkylation reactions of PhCH=CHCH(OAc)R, R = H, Me, Et, with the anion of dimethyl malonate. Modest to good selectivities are reported.

Original languageEnglish
Pages (from-to)4591-4597
Number of pages7
JournalOrganometallics
Volume18
Issue number22
Publication statusPublished - Oct 25 1999

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Maleic Anhydrides
Phosphites
alkylation
Alkylation
Palladium
Sulfides
anhydrides
palladium
Alkenes
chelates
Nuclear magnetic resonance spectroscopy
alkenes
Anions
selectivity
anions
Ligands
Derivatives
X ray diffraction
nuclear magnetic resonance
ligands

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Chiral Phosphite-Thioether Complexes of Palladium(0). Comments on the Pd, Rh, and Ir Regio-and-Enantioselective Allylic Alkylations of PhCH=CHCH(OAc)R, R = H, Me, Et. / Selvakumar, Kumaravel; Valentini, Massimiliano; Pregosin, Paul S.; Albinati, Alberto.

In: Organometallics, Vol. 18, No. 22, 25.10.1999, p. 4591-4597.

Research output: Contribution to journalArticle

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AB - The new chiral auxiliary (R)-2-ethylthio-1-(phenylethyl)-(R)-binaphthyl phosphite, 1, and three stable Pd(0) olefin complexes containing this chelate, 2-4, have been synthesized. The structure of the maleic anhydride complex 3 has been determined by X-ray diffraction methods. Solution details for 2-4 and aspects of their dynamics have been elucidated via 2-D NMR spectroscopy. The fumaronitrile complex 2 exchanges intramolecularly, whereas the maleic anhydride and pentenedione derivatives, 3 and 4, respectively, exchange intermolecularly. Ligand 1 has been used as auxiliary in the Pd, Rh, and Ir regio- and enantioselective allylic alkylation reactions of PhCH=CHCH(OAc)R, R = H, Me, Et, with the anion of dimethyl malonate. Modest to good selectivities are reported.

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